Hydrogenation catalyst



.Oct. 11, 1938. n I J. FRANCON 2,132,613

HYDROGENAT I ON CATALYS '1 Filed Sept. 28, 1935 INVENTOR'. Jacq es FRRNCON wronnsy Patented Oct. 11, 1938 UNITED STATES PATENT OFFICE 2,132,613 HDROGENATION CATALYST Jacques Franc-on, Paris, France, assignor to 80- cit Industrielle des Carburants ct Solvants, Ivry-sur-Seine, France Application September 28, 1935, Serial no. 42,674 In France October 5, 1934 2 Claims. I (O1- 23-236) The process forming the object of the present In Fig. 2, the heating oil flows through a heliinvention relates to a plant which can be used cal tube It mounted in the tube I. In Fig. 3, the for efiecting the catalytic hydrogenation, with tube 1 contains a nest of vertical tubes ll filled or without pressure, of gases and vapours resultwith the coils or gauzes 2, while the hot oil flows 5 ing from the carbonization of solid fuels or from around the said tubes 1 l. v 5 the pyrolysis of liquid fuels and their derivatives The processes which bring about this result such as: petroleums, tars, creosotes, coal oils and and which also form the subject-matter of the for the vaporization of some hydrocarbons such invention are characterized as follows: as benzols, naphthalene, anthracene and the like, lst-By the fact that the vapours of an orl0 for the purpose of obtaining, for example, Iormganometallic compound are conveyed through aldehyde. light hydrocarbons, naphthalene and the materials which are to be coated and kept anthracene hydrides and the like. under such conditions that the said vapours dis- The catalytic plant consists essentially of a. integrate and that the metal of which they are metallic tube, of a suitable thickness, having an composed is deposited upon the metallic or other effective length of about 6 meters and mainsupports. 15 tained at the required temperature (which can Nickel in a pulverulent state can thus be deposvary according to circumstances between 150 and ited upon coils or grates of nickel or upon grates 220 C.) by a circulation of superheated oil, either of iron, chromium or any other metal by proceedinternally by means of coils, or externally by ing as follows:

means of a double wall or in any other suitable A stream of carbon monoxide is caused to react 20 manner- The Said pp u s fill d With Simple, at a suitable temperatureabout 50 C.over double or treble concentric metallic coils or windreduced nickel; there being thus formed tetraings, from 50 to 60 m/m. long, 0 w t allic carbonyl of nickel Ni(CO)4 which is removed in gauzes rolled on themselves, formed of gauze the form of vapour by the excess of the gaseous strips or ribbons, from 20 to 35 m/m. wide and stream. The mixture is led over the metal grates 25 from 50 to 100 m/m. long; said 'gauzes are woven which are intended to be coated or covered, enwith meshes of suitable sizes; the wires or threads closed in a closed space and heated at a temperawhich constitute the coils or the gauzesare comture higher than 100 C. Under these condiposed of wires of nickel, iron, chromium, or an tions, the tetracarbonyl of nickel is destroyed:

alloy of two or three of said metals. The said Ni(C0) 4=4CO+Ni and the metal is deposited 30 gauzes or the said coils or windings constitute upon the grates or upon the coils or windings. the metallic support of the catalytic metals. It Proceeding by the same way, it is possible to is necessary to cover the said support either with obtain deposits of ironor cobalt, by starting from a similar metal or with any other metal, in a cobalt and iron carbonyl; deposits of lead, by

porous state, in order to obtain a catalytic action. starting from tetraethyl lead; deposits of tin, 35

In the accompanying drawing, Fig. 1 is avertizinc, silicon and of all metals by starting from cal section of an embodiment of a catalyzing their organic compounds.

device adapted fo ca y out the method de- 2ndBy the fact that the support is lined with scribed herein; or embedded in a paste of nickel hydrate by com- 40 Figs. 2 and 3 are similar views respectively of plying with the following procedure. In order to 44} modified forms of the device. obtain 1 kilog. of paste of hydrate of nickel which In all the figures, l is the metallic tube filled must contain from about 12% of nickel oxides with metallic coils or gauzes 2. The gases or (that is to say 9.5% of pure nickel), 95 grams of vapours to be hydrogenized enter at 3 and after pure nickel are treated, the same being in the 45 having passed through the chamber filled with form of powder, threads or wires, or in lumpsj 45 the coils or gauzes the said gases or vapours leave the same are attacked by 250 cubic centimeters t l, of pure nitric acid at 40 which are diluted in 250 The tube i is heated by ,a stream of hot oil. In cubic centimeters of water; said action being cf- Fig. 1, the tube l is surrounded by a casing or iected by heat treatment or preferably by the cold jacket 5 separated from the tube I by an annular method. When the operation is completed, the 50 space in which is placed a helical guide 6. The product is filtered if required. hot oil enters at I, streams around the tube l The solution of nitrate of nickel thus obtained along a helical path and leaves at 8. A grid 9 is diluted in a receptacle with from 40 to 50 liters mounted in the tube l supports the metallic coils of water; the same is dissolved by means of a u or gauzes 2. solution of caustic soda at 10% while stirring frequently and until a slightly alkaline reaction with litmus paper is obtained. Then the product is allowed to rest and the liquid which floats and which contains the nitrate of sodium is decanted by syphonage. The receptacle is again filled with water, the whole is stirred and decanted and the operation is repeated from 5 to 6 times in order to give a well washed hydrate. For the purpose of ascertaining whether the paste of hydrate of nickel has been sufllciently washed, there is introduced into a test tube a few cubic centimeters of a solution of a ferrous salt, then very slowly and with care, a few cubic centimeters of the washing water to be examined are supplied, the two liquids being of a diiferent density are clearly separated. Through a graduated cylinder, a few dropsaof sulphuric acid are caused to arrive at the point of contact between the two liquids; when the hydrate is sufllciently washed, no colouration will occur; but if not sufilciently washed, a brownish colouration will appear.

The paste having been suillciently washed, the same is thrown upon a wire gauze and left to drip until it is sufficiently dry. It is also possible to operate with a filter undergoing the action of vacuum or a filter-press. Every one of the following metals are added to the nickel in the ratio of l to 2% of its weight: silver, vanadium, cobalt, cadmium or their alloy which has previously been dissolved in nitric acid and precipitated by soda under the same conditions.

Said paste is thoroughly mixed with the supports or carriers, coils or gauzes,'previously oxidized by heat treatment, either under the action of air or under the action of steam. or bya mixeous compound upon tureofbothandthecatalyaerisfllledwiththe said mixture.

The best mixture is obtained when the weight of the supports or carriers and the weight of the metals are in the proportions of 90 to 10.

The foregoing procedure effects the deposit upon any metallic or other support of pulveruient and porous metals, capable of catalytic action.

The catalyzer is reduced at a temperature ranging between 240 and 280 6., by causing dry hydrogen to pass during a period of to hours.

I claim:

1. A process for depositing catalytic metals on metallic supports, comprising heating the said metallic supports at a temperature above 100 C. and leading a gaseous organo-metallic compound over the heated metallic supports, so as to cause decomposition of the said gaseous organo-metallic compound at the surface of the heated metallic supports and precipitation of the metal contained in the gaseous compound upon the said ing heating the said metallic supports at a temperature above 100" C. and leading over the same a gaseous organic compound of a metal selected from a group comprising nickel, iron, chromium, cobalt, lead, tin, zinc and silicon so as to cause decomposition of the said gaseous compound at the surface of the heated metallic supports and precipitation of the metal contained in said gasthe said metallic supports. JACQUES FRANCON. 

